Method of removing mercaptans from hydrocarbon oil



Patented Oct. 17, 1944 2,360,537 I C E METHODjOF REMOVING MERCAPTANS FROM HYDROCARBON on.

George W. Ayers, Chicago, and Lawrence M. Henderson, Winnetka, Ill., assignors to The Pure Oil Company, Chicago, Ill., a corporation of Ohio No Drawing. Application March 17, 1943,

Serial No. 479,534

6 Claims.

This invention relates to the removal of weakly acidic bodies from substantially neutral waterimmiscible organic liquids and is more particularly concerned with the removal of mercaptans from hydrocarbon oils such as gasoline.

In Patent 2,297,621 there is disclosed a process for the removal of weakly acidic bodies, such as mercaptans from hydrocarbon liquids, by means of aqueous solutions of caustic alkali containing alkali metal naphthenates and a solventizer therefor, The process covered by the claimsof this patent is known as the Mercapsol process and the treating solution is known as the Mer capsol solution.

The effectiveness of Mercapsol solutions for removing or extracting mercaptans from hydrocarbon oil generally varies directly with the concentration of free alkali and alkali metal naphthenates in the solution. Thus, more concentrated alkali solutions containing higher concentrations of alkali metal naphthenates remove larger amounts of mercaptans from gasoline or other hydrocarbons. However, there is a practical limit to the concentration of both the free alkali and the alkali metal naphthenates in the treating solution due to the fact that as the concentrations of the two are increased the naphthenates precipitate out of solution. A further reason why the concentration of these ingredients must be limited is that at lower temperatures precipitation of naphthenates from the solution occurred. Although a solution-may be satisfactory under summer operating conditions, a drop in atmospheric temperature will cause precipitation in the solution. Furthermore, as concentration of-free alkali and alkali metal naphthenates increase the viscosity of the treating solution increases to a point where the solution cannot be readily handled and causes emulsion difficulties 'when mixed with thehydrocarbon oil to be treated.

We' have discovered that the effectiveness of I Mercapsol and other solutions containing solu-' bility promoters, for extracting mercaptans from hydrocarbon oils, can be considerably enhanced by adding thereto certain glycols. The addition of the glycols contemplated by the invention does not deleteriously affect the phys cal characteris tics of the treating solution when added in] amounts which are compatible with the treating solution. I r z An object of this inventioniis to 'providean 1 improvedv process for'extracting weakly acidic bodies from otherwise neutral water-immiscible organic liquids.

from hydrocarbon oils such as gasoline.

Still another object ofthe invention is to'provide a method of improving :theability of Mercapsol solution to extract acidic bodies such as mercaptans from otherwise neutral water-immiscible organic liquids such as hydrocarbon oils.

A further object of the invention is to provide an improved reagent for extracting weakly acidic bodies such as mercaptans from otherwise neutral Water-immiscible organic liquids such as hydrocarbon oils.

Other objects of our invention will become apparent from the following description.

In accordance with our invention we add to Mercapsol solution one or more glycols selected from the group consisting of triethylene glycol, propylene glycol and butylene glycols, including 1,3 butylene and isobutylene glycols. Solutions in accordance with our invention may be prepared by mixing together in proper proportions water, alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, naphthenic acids, solventizer such as phenol or cresol and one or more glycols from the aforesaidgroup. It will be apparent that the naphthenic acids and the amount of solventizer which may be used must be i at leastsuflicient to keep the naphthenates in solution. The amount of'glycol may vary from 1% up to 20%, but in no case should be more than the amount which is compatible with the.

solution. We have found that an amount of free alkali i. e. alkali metal hydroxide over and above that necessary to react with ingredients in the treating solution, between 10 and 20% by weight and a concentration of from 15 to 25% of alkali metal naphthenates gives good results.

In order to demonstrate the effectiveness of adding the aforesaid glycols to Mercapsol solution, a series of solutions was prepared and tested on mercaptan-containing gasoline produced by high pressure thermal cracking on petroleum oil. The Mercapsol solution used in the tests was made by mixing together the following ingredients:

Per cent byweight Sodium hydroxide 18.3 Naphthenic acids (240-260XX) 18.6 Meta-para cresol 6.4

Water 56.?

The naphthenic acids used in preparing this solution correspond to those given under column 2, Table II, on page 3 of Henderson et al. Patent No. 2,297,621. The free sodium hydroxide con for 15 minutes in an atmosphere of nitrogen with 2.1 cc. of the respective treating solution. The mercaptan and disulfide sulfur Was determined on the gasoline immediately before and after the treatment with the treating solution. The results from the various tests made are tabulated in the following table:

connection with the enhancing of Mercapsol solution by means of the addition of certain glycols, the invention is also applicable to enhancing the mercaptan extracting ability of aqueous Treating solution No.

Mercapsol with 7% by wt. oi dipropylcne glycol Mercapsol with 14% by Wt. of glycerine Mercapsol with 7% by Wt. of sorbitol Mercapsol Mercapsol with 14% by wt. of triethylene glycol Mercapsol with 14% by wt. of propylene glycol. Mercapsol with 14% by wt. of 1,3-butylene glycol 87.4% by wt. 1110, 12.6% by wt. NaOH Mercapsol 86.0% by wt. H10, 14.0% by wt. of propylene glycoL.

73.4% by wt. H2O, 12.6% by wt. NaOH, 14.0% by wt pylene glycol 59.3% by wt. H10, 12 6% by wt. NaOH, 28.1% by propylene glycol 85% by Wli.H2O,15% by wt. NaOH -1 Mercapsol with 7% by wt. of 2-methyl-pentanediol-2,4

Mercapsol with 14% by wt. of isobutylene glycol Mercapsol with 7% by wt. of hexamethylcne glycol.

' 71.9% by wt. 1120, 28.1% by wt. of propylene glycol pro- Mercapsol with l4% by wt. of propylene glycol 5 alkali solutions containing other solubility promotors, particularly phenolic and/or naphthenic constituents recovered as acid 011 from spent caustic alkali solution used in the washing of petroleum oils and distillates. Acid oils sprung from spent caustic soda by means of neutrali zation with acid or acid anhydride such as carbon dioxide have the ability to act as solubility promoters to enhance the ability of caustic alkali in extracting mercaptans from gasoline and other hydrocarbon oils. The ability of these acid oils to enhance the mercaptan extracting ability of caustic alkali solutions is increased by the addition of glycols selected from the group consist- Percent Iner- Percent mer- Percent di- Percent di- P r t captan s in captan s in sulfide s in sulfide s in 9 untreated treated untreated treated lsnercap s gasoline gasoline gasoline gasoline remove e 0. 0189 0.0095 0.0048 0.0044 49.7 0. 0189 0. 0055 0. 0048 0. 0058 05. 0 0. 0189 0. 0042 0. 0048 0. 0037 77. 7 9 0. 0189 0. 0035 0. 0048 0. 0001 74. 0 0. 0189 0. 0051 0. 0048 0. 0073 59. 7 0. 0189 0. 0042 0. 0048 0. 0077 02. 4 0. 0189 0. 0004 0. 0048 0. 0001 59. 3 0. 0189 0. 0002 0. 0048 0. 0058 02. 0 0. 0189 0. 0044 0. 0048 0. 0079 60. 3 0. 0189 0. 0004 0. 0048 0. 0057 01. 3 0. 0189 0. 0059 0. 0048 0. 0084 49. 8 0. 0189 0. 0062 0. 0048 0. 0080 50. 2 0. 0189 0. 0000 0. 0048 0. 0084 40. 0 0. 0325 0. 0149 0. 0011 0. 0031 48. 0 0. 0325 0. 0093 0.0011 0. 0034 04. 0 0.0325 0. 0001 0.0011 0. 0003 05. 2 0. 0325 0. 0053 0.0011 0. 0034 70. 8 0. 0325 0. 0054 0. 0011 0. 0044 73. 2 0.0325 0. 0052 0.0011 0. 0058 09. 5 0. 0325 0. 0075 0.0011 0. 0058 02. 5 0. 0330 0. 0135 0. 002 0.003 50.1 0. 0330 0. 0102 0.002 0. 003 00.1 0. 0330 0. 0330 0.002 0. 003 None.

. 0. 0330 0. 0325 0. 002 0. 003 None.

From the series of treatments, Nos. 1 to 13, it will be seen that Mercapsol solution extracted considerably more mercaptan from the gasoline than did straight caustic soda solution. The results further show that the addition of triethylene glycol and propylene glycol further enhance the ability of the Mercapsol solution to extract mercaptans from the gasoline, whereas the addition of ethylene glycol, diethylene glycol, tetraethylene glycol and dipropylene glycol detracted from the ability of the Mercapsol to extract mercaptans. The same is true of other polyhydroxy alcohols such as 2-methyl-pentanediol-2,4, glycerine, sorbitol, mannitol and dextrose.

In the series of tests including Nos, 14 to triethylene glycol, propylene glycol, 1,3-butylene glycol and isobutylene glycol all enhance the mercaptan extracting ability of Mercapsol, whereas hexamethylene glycol detracted from the ability of Mercapsol solution to extract mercaptans from gasoline.

The series of treatments Nos. 21 to 2'7 show that propylene glycol in the absence of Mercapsol detracts from the ability of caustic soda solution to extract mercaptans from gasoline. This fact serves to emphasize the unexpected result obtained by mixing propylene glycol and the other glycols covered by this invention with Mercapsol.

Although we have described our invention in ing of propylene glycol, triethylene glycol and butylene glycols.

Similarly, used or aqueous spent caustic alkali solutions which have been regenerated and in which have been concentrated acid constituents extracted from petroleum oils can be enhanced by adding thereto one or more glycols selected from the aforementioned group.

Although we have used 7% by volume of treating solution based on the gasoline treated in the examples herein set forth, larger or smaller amount of treating solution may be used depending on the nature and amount of acidic bodies or mercaptans contained in the gasoline or other organic liquid and the completeness of extraction desired. From 5% to about 20% by volume of treating solution is sufiicient for treating most types of liquids.

We claim:

1. The method of removing mercaptans from hydrocarbon oil which comprises contacting said oil with an aqueous solution containing not less than 5% by weight of free alkali metal hydroxide, not less than about 10% by weight of alkali metal naphthenate salts, a solventizer for said salts and a glycol selected from the group consisting of triethylene glycol, propylene glycol and butylene glycols, said glycol being present in amounts not less than about 1% by weight.

2. Method in accordance with claim 1 in which the glycol is triethylene glycol.

3. Method in accordance with claim 1 in which the glycol is propylene glycol.

4. Method in accordance with claim 1 in which the glycol is 1,3-butylene glycol.

5. The method of extracting mercaptans from gasoline which comprises contacting said gasoline with an aqueous solution containing from about 5% to 20% of free alkali metal hydroxide selected from the group consisting of sodium and potassium hydroxides, from about 10 to 25% of alkali metal naphthenates, a solventizer for said naphthenates, selected from the group consisting of alkali metal phenolates and cresolates in amount suflicient to keep the naphthenates in solution and from about 1 to 20% of a glycol selected from the group consisting of triethylene glycol, propylene glycol and butylene glycols.

6. The method of removing mercaptans from hydrocarbon oil comprising contacting said oil with an aqueous solution containing approximately 10-20% of free alkali metal hydroxide, an amount of alkali metal naphthenates in excess of that which is soluble in the alkali solution in the absence of a solventizer and suflicient to enhance the mercaptan extracting ability of the alkali solution, suflicient solventizer to keep the naphthenates in solution and a glycol selected from the group consisting of triethylene glycol, propylene glycol and butylene glycols, said 

